Amorphous ionically conductive metal oxides and sol gel method of preparation

ABSTRACT

Amorphous lithium lanthanum zirconium oxide (LLZO) is formed as an ionically-conductive electrolyte medium. The LLZO comprises by percentage of total number of atoms from about 0.1% to about 50% lithium, from about 0.1% to about 25% lanthanum, from about 0.1% to about 25% zirconium, from about 30% to about 70% oxygen and from 0.0% to about 25% carbon. At least one layer of amorphous LLZO may be formed through a sol-gel process wherein quantities of lanthanum methoxyethoxide, lithium butoxide and zirconium butoxide are dissolved in an alcohol-based solvent to form a mixture which is dispensed into a substantially planar configuration, transitioned through a gel phase, dried and cured to a substantially dry phase.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 12/848,991, filed Aug. 2, 2010, which is a continuation-in-partof U.S. patent application Ser. No. 12/163,044 filed Jun. 27, 2008,which claims priority to U.S. Provisional Application No. 60/947,016,filed Jun. 29, 2007, the entirety of which are hereby incorporated byreference.

BACKGROUND OF THE INVENTION

A battery cell is a useful article that provides stored electricalenergy that can be used to energize a multitude of devices, particularlyportable devices that require an electrical power source. The cell is anelectrochemical apparatus typically formed of at least oneion-conductive electrolyte medium disposed between a pair ofspaced-apart electrodes commonly known as an anode and a cathode.Electrons flow through an external circuit connected between the anodeand cathode. The electron flow is caused by the chemical-reaction-basedelectric potential difference between the active anode material andactive cathode material. The flow of electrons through the externalcircuit is accompanied by ions being conducted through the electrolytebetween the electrodes.

Electrode and electrolyte cell components typically are chosen toprovide the most effective and efficient battery for a particularpurpose. Lithium is a desirable active anode material because of itslight weight and characteristic of providing a favorable reductionpotential with several active cathode materials. Liquid and aqueouselectrolytes have often been chosen because of favorable ion-conductingcapabilities. Despite the benefits provided by certain anode materialsand electrolytes, the materials themselves and, often, the combinationof a particular electrode material and a particular electrolyte cancause problems in cell performance and, in some instances, can create ahazardous condition. For example, as advantageous as lithium can be asan active anode material, it can be degraded and otherwise reactundesirably with such common mediums as air and water, and certainsolvents. As a further example of problems, certain liquids that areuseful as effective electrolytes can create hazardous conditions whenserving as components of a lithium-ion battery.

For the reasons broadly stated above, it is often desirable to use anon-aqueous and non-liquid electrolyte medium in cells. Non-aqueouselectrolyte mediums are desired because water can interact undesirablywith some desirable electrode materials such as lithium. Non-liquidelectrolyte mediums are desired for several reasons. One reason is thatliquid electrolytes often react detrimentally with desirable electrodesubstances such as lithium even though the liquid is non-aqueous.Another reason that liquid electrolytes can be undesirable is the needto prevent electrolytic material from freely flowing beyond apredetermined geometric boundary configuration. For example, leakage ofelectrolyte solution from the battery container is typicallyundesirable. Another problem with liquid electrolytes is that somesolvents that are used as effective non-aqueous, liquid electrolytes areflammable and have a relatively high vapor pressure. The combination offlammability and high-vapor pressure creates a likelihood of combustion.Further in this regard, batteries that use lithium-based anodes can posesevere safety issues due to the combination of a highly volatile,combustible electrolyte and the active nature of lithium metal.

Some of the problems associated with particular cell electrodes andelectrolyte can result in internal failure of the cell. One type ofinternal failure is the discharge of electric current internally, withinthe cell, rather than externally of the cell. Internal discharge mayalso be referred to as “self-discharge.” Self-discharge can result inhigh current generation, overheating and ultimately, a fire. A primarycause of self-discharge has been dendritic lithium growth duringrecharge of a rechargeable battery. In rechargeable cells having lithiumanodes, dendrites are protuberances extending from the anode base thatare formed during imperfect re-plating of the anode during recharge.Dendrites or growths resulting from low-density lithium plating duringrecharge can grow through the separator that separates anode fromcathode particularly if the separator is porous or solid but easilypunctured by the growth. When the growths extend far enough tointerconnect the anode and cathode, an internal electrical short circuitis created through which current can flow. Electrical current producesheat that will vaporize a volatile electrolyte substance. In turn,vaporization of the electrolyte can produce extreme pressure within thebattery housing or casing which can ultimately lead to rupture of thehousing or casing. The temperatures that result from an electrical shortcircuit within a battery are sometimes high enough to ignite escapingelectrolyte vapors thereby causing continuing degradation and therelease of violent levels of energy. Lithium-ion batteries weredeveloped to eliminate dendritic lithium growth by utilizing the lithiumions inserted into graphite anodes rather than re-platable lithium metalanodes. Although these lithium-ion batteries are much safer than earlierdesigns, violent failures still occur.

Ion-conductive, solid-glass electrolytes and ceramic electrolytes havebeen developed in the past to address the need for an electrolyte mediumwithout the shortcomings described above. These solutions have includedglass electrolyte materials such as Lithium Phosphorous Oxy-Nitride(LiPON) and a class of glass-ceramic materials generally referred to asLiSICON (an acronym for Lithium Super-Ionic Conductor) structure-typematerials and NaSICON (an acronym for Sodium Super-Ionic Conductor,wherein the “Na” portion of the acronym is the chemical symbol forsodium) structure-type materials. However, these materials havelimitations. LiPON has low ionic conductivity, in the range of 1.2E−6S/cm, and generally can only be applied or used as thin films less than10 μm thick. In addition, it has to be produced using a reactivesputtering process in a low vacuum environment which can be veryexpensive. LiPON is also unstable in contact with water which eliminatesits possible use as a protective electrolyte in battery systems whereexposure to moisture or ambient air may occur. On the other hand LiSICONand NaSICON structure-type materials are stable in contact with waterbut are unstable in contact with lithium. When in contact with lithiumthis class of materials turns dark and can conduct electric current byelectron flow thus minimizing usefulness as electrolyte separators.

Thus it can be appreciated that it would be useful to have a cellelectrolyte medium that is a conductor of ions, that is protective ofand stable in contact with lithium, that is non-aqueous, that isnon-liquid, that is non-flammable, and that does not produce shortcircuits that are associated with dendritic plating of lithium.

BRIEF SUMMARY OF THE INVENTION

According to a first embodiment the invention provides an amorphousoxide-based compound having a general formulaM_(w)M′_(x)M″_(y)M′″_(z)C_(a),

wherein M is at least one alkali metal;

M′ is at least one metal selected from the group consisting oflanthanides, barium, strontium, calcium, indium, magnesium, yttrium,scandium, chromium, aluminum, and alkali metals, provided that when M′is an alkali metal, M′ further contains at least one non-alkali M′metal;

M″ is at least one metal selected from the group consisting ofzirconium, tantalum, niobium, antimony, tin, hafnium, bismuth, tungsten,silicon, selenium, gallium and germanium;

M′″ comprises oxygen and optionally at least one element selected fromthe group consisting of sulfur and halogens; and

w, x, y, and z are positive numbers, including various combinations ofintegers and fractions or decimals, and “a” may be zero or a positivenumber.

In accordance with an aspect of the first embodiment, M compriseslithium, M′ comprises lanthanum, M″ comprises zirconium, and M′″comprises oxygen.

In accordance with another aspect of the first embodiment, by percentageof total number of atoms, M comprises from about 0.1% to about 50%, M′comprises from about 0.1% to about 25%, M″ comprises from about 0.1% toabout 25%, M′″ comprises from about 30% to about 70%, and carboncomprises from 0.0% to about 25%.

According to a second embodiment of the present invention, anelectrolyte medium for an electrochemical cell comprises a layer ofamorphous lithium lanthanum zirconium oxide.

In accordance with an aspect of the second embodiment, the layer ofamorphous lithium lanthanum zirconium oxide comprises by percentage oftotal number of atoms from about 0.1% to about 50% lithium, from about0.1% to about 25% lanthanum, from about 0.1% to about 25% zirconium,from about 30% to about 70% oxygen and from 0.0% to about 25% carbon.

According to a third embodiment of the present invention, a method forsynthesizing an amorphous oxide-based compound comprises

substantially dissolving in a quantity of an alcohol-based solvent toproduce a mixture, quantities of an alkoxide of at least onealkali-metal, an alkoxide of at least one metal selected from the groupconsisting of lanthanides, barium, strontium, calcium, indium,magnesium, yttrium, scandium, chromium, aluminum, and alkali metals,provided that when the metal is an alkali metal, it further contains atleast one metal selected from lanthanides, barium, strontium, calcium,indium, magnesium, yttrium, scandium, chromium, and aluminum; analkoxide of at least one metal selected from the group consisting ofzirconium, tantalum, niobium, antimony, tin, hafnium, bismuth, tungsten,silicon, selenium, gallium and germanium; and optionally analcohol-soluble precursor of at least one of sulfur, selenium, and ahalogen,

dispensing said mixture in a substantially planar configuration,transitioning through a gel phase, and drying and curing to asubstantially dry phase.

According to a fourth embodiment of the invention, amorphous lithiumlanthanum zirconium oxide is synthesized by substantially dissolvingquantities of a lanthanum alkoxide, a lithium alkoxide, and a zirconiumalkoxide in a quantity of an alcohol-based solvent to produce a mixture;then dispensing the mixture into a substantially planar configuration,transitioning through a gel phase, and drying and curing to asubstantially dry phase.

In accordance with an aspect of the fourth embodiment, the alcohol-basedsolvent comprises methoxyethanol.

In accordance with another aspect of the fourth embodiment, thelanthanum alkoxide comprises lanthanum methoxyethoxide, the lithiumalkoxide comprises lithium butoxide and the zirconium alkoxide compriseszirconium butoxide.

In accordance with yet another aspect of the fourth embodiment, thequantity of lanthanum methoxyethoxide comprises an amount of lanthanummethoxyethoxide pre-dissolved in an amount of the alcohol-based solventto produce a lanthanum methoxyethoxide solution comprising about 12% byweight lanthanum methoxyethoxide.

In accordance with an additional aspect of the fourth embodiment, thequantity of zirconium butoxide comprises an amount of zirconium butoxidepre-dissolved in an amount of butanol to produce a zirconium butoxidesolution comprising about 80% by weight said zirconium butoxide.

In accordance with yet an additional aspect of the fourth embodiment,the quantity of lanthanum methoxyethoxide comprises about 4.5 grams ofthe lanthanum methoxyethoxide solution, the quantity of lithium butoxidecomprises about 0.65 grams thereof, the quantity of zirconium butoxidecomprises about 0.77 grams of the zirconium butoxide solution and thealcohol-based solvent comprises about 5 grams of methoxyethanol.

In accordance with a further aspect of the fourth embodiment, themixture is dispensed into a substantially planar configuration by one ofspin coating, casting, dip coating, spray coating, screen printing orink-jet printing.

According to a fifth embodiment of the invention, amorphous lithiumlanthanum zirconium oxide is synthesized by substantially dissolvingquantities of a lanthanum alkoxide, a lithium alkoxide, a zirconiumalkoxide and a polymer in a quantity of an alcohol-based solvent toproduce a mixture; then dispensing the mixture into a substantiallyplanar configuration, transitioning through a gel phase, and drying andcuring to a substantially dry phase.

In accordance with an aspect of the fifth embodiment, the alcohol-basedsolvent comprises methoxyethanol and the polymer comprises polyvinylpyrrolidone.

In accordance with another aspect of the fifth embodiment, the lithiumalkoxide comprises lithium butoxide, the lanthanum alkoxide compriseslanthanum methoxyethoxide, and the zirconium alkoxide compriseszirconium butoxide.

In accordance with yet another aspect of the fifth embodiment, thequantity of lanthanum methoxyethoxide comprises an amount of lanthanummethoxyethoxide pre-dissolved in an amount of the alcohol-based solventto produce a lanthanum methoxyethoxide solution comprising about 12% byweight lanthanum methoxyethoxide.

In accordance with an additional aspect of the fifth embodiment, thequantity of zirconium butoxide comprises an amount of zirconium butoxidepre-dissolved in an amount of butanol to produce a zirconium butoxidesolution comprising about 80% by weight said zirconium butoxide.

In accordance with yet another additional aspect of the fifthembodiment, the quantity of polymer comprises an amount of polymerpre-dissolved in an amount of alcohol-based solvent to produce a polymersolution

In accordance with a further aspect of the fifth embodiment, thequantity of lanthanum methoxyethoxide comprises about 4.5 grams oflanthanum methoxyethoxide solution, the quantity of lithium butoxidecomprises about 0.65 grams thereof, the quantity of zirconium butoxidecomprises about 0.77 grams of said zirconium butoxide solution, thequantity of polymer solution comprises not more than about 2 grams ofpolyvinyl pyrrolidone dissolved in about 5 grams of methoxyethanol, andthe quantity of alcohol-based solvent comprises about 5 grams ofmethoxyethanol.

In accordance with yet a further aspect of the fifth embodiment, themixture is dispensed into a substantially planar configuration by one ofspin coating, casting, dip coating, spray coating, screen printing orink-jet printing.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

The foregoing summary, as well as the following detailed description ofthe invention, will be better understood when read in conjunction withthe appended drawings. For the purpose of illustrating the invention,there are shown in the drawings embodiments which are presentlypreferred. It should be understood, however, that the invention is notlimited to the precise arrangements and instrumentalities shown.

In the drawings:

FIG. 1 is schematic representation of a cell suitable for incorporatingan electrolyte medium in accordance with the present invention;

FIG. 2 depicts XPS Spectra Graphs for amorphous LLZO films according toan embodiment of the invention;

FIG. 3 depicts EIS spectra of amorphous LLZO films according to anembodiment of the invention;

FIG. 4 is a Nyquist plot of the full EIS spectrum of an amorphous LLZOfilm with partial substitution by aluminum according to an embodiment ofthe invention;

FIG. 5 is a Nyquist plot of an amorphous LLZO film with partialsubstitution by aluminum according to an embodiment of the inventionfocusing on high frequency real axis intercept;

FIG. 6 is a Nyquist plot of the full EIS spectra of an amorphous LLZOfilm with addition of acetylacetonate according to an embodiment of theinvention; and

FIG. 7 is a Nyquist plot of an amorphous LLZO film with addition ofacetylacetonate according to an embodiment of the invention focusing onhigh frequency real axis intercept.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to ionically-conductive materials useful aselectrolyte mediums in electrochemical cells, and more particularly, theinvention relates to an ionically-conductive amorphous lithium lanthanumzirconium oxide composition formable as an electrolyte medium for anelectrochemical cell such as a battery cell.

Embodiments of the present invention are described herein. The disclosedembodiments are merely exemplary of the invention that may be embodiedin various and alternative forms, and combinations thereof. As usedherein, the word “exemplary” is used expansively to refer to embodimentsthat serve as illustrations, specimens, models, or patterns. The figuresare not necessarily to scale and some features may be exaggerated orminimized to show details of particular components. In other instances,well-known components, systems, materials, or methods have not beendescribed in detail in order to avoid obscuring the present invention.Therefore, at least some specific structural and functional detailsdisclosed herein are not to be interpreted as limiting, but merely as abasis for the claims and as a representative basis for teaching oneskilled in the art to variously employ the present invention.

Referring to FIG. 1, therein is illustrated a cross-sectional, schematicrepresentation of a battery cell, or electrochemical cell, 10 suitablefor incorporating an electrolyte medium in accordance with the presentinvention. A centrally-disposed cathode current collector 11 is flankedon either side by a cathode 12. An electrolyte medium 13 is disposed ina U-shaped, face-contacting relationship with the cathodes 12. An anode14 is disposed in a U-shaped, face-contacting relationship with theelectrolyte medium 13. An anode current collector 15 is disposed in aU-shaped, face-contacting relationship with the anode 14. A cathodeterminal 16 is disposed in contacting relationship with the cathodecurrent collector 11 and cathode 12.

Overview

Lithium is a desirable substance to use as an electrode (particularly ananode) in a cell. This is because lithium is one of the lightest ofelements, while possessing high energy density and high specific energy.However, lithium is extremely undesirably reactive with water and islikewise undesirably reactive with many highly ionically-conductiveliquid electrolytes. Thus, it is desirable to have an electrolyte mediumthat is non-aqueous and non-liquid so as to be compatible withelectrodes containing or consisting of lithium. A solid electrolyte isnon-aqueous and non-liquid; however, some solid electrolytes still reactundesirably with lithium. Thus, it is desirable to have an electrolytemedium that not only is non-aqueous and non-liquid but that is alsootherwise compatible with electrodes that contain or comprise lithium.

Often, batteries are used in applications that require unique geometriesand physical specifications for the battery package. For example,batteries are used in very small electronic devices that requirebatteries to be sized on the order of millimeters or less. Forapplications requiring batteries of very small dimensions, it isimportant that the components of these battery cells perform effectivelyeven though produced at a very small size. Thus, it is important to havean electrolyte medium that is effective even though produced on anextremely small scale.

One method of producing cells of very small dimensions is to constructwhat are known as “thin-film” batteries. Typically, in thin-film batterycells the electrodes and electrolyte medium comprise substrates having athin, film-like configuration. Thin-film batteries also have theadvantage of potentially being flexible. The electrolyte medium forthin-film battery cells has to be effective even though produced at verysmall dimensions.

The Invention in Detail

The invention is an effective, ionically-conductive composition for anelectrolyte medium. The invention further encompasses a method forproducing the composition in general and a method for forming anelectrolyte medium comprising the composition. The electrolyte mediumtaught by the invention is non-aqueous, non-liquid, inorganic, andcompatible with lithium and lithium-containing compositions, and can bemanufactured in thin-dimensioned and small-dimensioned configurations.

In an embodiment, the composition of the invention is amorphous lithiumlanthanum zirconium oxide (for convenience, sometimes this compositionis referred to herein as “LLZO”). As explained in more detail below,amorphous LLZO prepared by the method of the invention often containscarbon and thus is more properly named lithium carbon lanthanumzirconium oxide (LCLZO). For the purposes of this disclosure, the term“LLZO” may be understood to refer to LLZO and/or LCLZO. The amorphousLLZO is highly ionically-conductive. It is inorganic and compatible withlithium. It can be used to produce a solid, thin-film electrolyte mediumthat facilitates incorporation into a small-dimensioned energy cell.

The amorphous LLZO is unique as an electrolyte medium as well as in andof itself The invention teaches that the amorphous compound may have achemical make-up wherein certain other elements may be partially orfully substituted for the four primary constituent elements lithium,lanthanum, zirconium and oxygen. Substitutes for the lithium constituentinclude elements in the alkali-metal family of the Periodic Table.Substitutes for the lanthanum constituent include barium, strontium,calcium, indium, magnesium, yttrium, scandium, chromium, aluminum,elements in the alkali-metal family of the Periodic Table and elementsin the lanthanide series of the Periodic Table. Substitutes for thezirconium constituent include tantalum, niobium, antimony, tin, hafnium,bismuth, tungsten, silicon, selenium, gallium and germanium. Substitutesfor the oxygen constituent include sulfur, selenium, and elements in thehalogen family of the Periodic Table.

In an embodiment, an amorphous compound has a general formulaM_(w)M′_(x)M″_(y)M′″_(z)C_(a) wherein M is at least one alkali metal;

M′ is at least one metal selected from the group consisting oflanthanides, barium, strontium, calcium, indium, magnesium, yttrium,scandium, chromium, aluminum, and alkali metals, provided that when M′is an alkali metal, M′ further contains at least one non-alkali M′metal;

M″ is at least one metal selected from the group consisting ofzirconium, tantalum, niobium, antimony, tin, hafnium, bismuth, tungsten,silicon, selenium, gallium and germanium;

M′″ comprises oxygen and optionally at least one element selected fromthe group consisting of sulfur and halogens; and

w, x, y, and z are positive numbers, including various combinations ofintegers and fractions or decimals, and “a” may be zero or a positivenumber. When “a” is zero, the compound has general formulaM_(w)M′_(x)M″_(y)M′″_(z).

The amorphous compound of the invention can be produced by a relativelysimple and inexpensive process. One broad category of process is asol-gel class of process. In an embodiment, the invention teachesadaptation of a sol-gel technique, which is generally known inchemistry, to form the ultimate, substantially solid compound and mediumof the invention. In the invention's application of a sol-gel process aprecursor solution mixture is derived from substantial dissolution ofliquid or/and solid solutes in a solvent. The sol-gel technique isadvantageous because it is not necessary to subject the amorphous-LLZOprecursor ingredients to extreme high temperatures as is necessary inthe case of solid-state reactions and other processes for producingsolid-electrolyte mediums. Extreme high temperatures are unwantedbecause such temperatures can produce undesirable effects in electrolytemembranes that are formed and/or in associated components.

In an embodiment, the amorphous compound of the invention is createdthrough a sol-gel methodology by processing alkoxides that containdesired end constituent elements. In an embodiment of methodology of theinvention, alkoxides of each of four primary constituents describedabove are dissolved in a quantity of an alcohol-based solvent to producea mixture; the mixture is dispensed in a substantially planarconfiguration, transitioned through a gel phase, and dried and cured toa substantially dry phase.

In an embodiment, alkoxides of other elements may be substituted for thefour primary constituent element alkoxides. Thus, in an embodiment, anamorphous compound is synthesized by substantially dissolving quantitiesof

an alkoxide of at least one alkali-metal,

an alkoxide of at least one metal selected from the group consisting ofbarium, strontium, calcium, indium, magnesium, yttrium, scandium,chromium, aluminum, alkali-metals, and the lanthanides,

an alkoxide of at least one metal selected from the group consisting ofzirconium, tantalum, niobium, antimony, tin, hafnium, bismuth, tungsten,silicon, selenium, gallium and germanium, and

optionally an alcohol-soluble precursor of at least one of sulfur,selenium, and a halogen, in a quantity of an alcohol-based solvent toproduce a mixture; dispensing the mixture in a substantially planarconfiguration, transitioning through a gel phase, and drying and curingto a substantially dry phase.

While the process has been described with respect to metal alkoxides asprecursors, the method of the invention is not limited to such metalcompounds. Rather, it is also within the scope of the invention toutilize other alcohol soluble precursor compounds which promote theformation of the desired metal oxide in a sol-gel process, such as, butnot limited to, metal β-diketonates. For example, metal acetylacetonate(metal acac) may be used as the metal source in the precursor solution.

It is also within the scope of the invention to include additionalcomponents in the precursor solution, such as acetic acid, ethanol, anethanol/water mixture, and acetylacetone (acac). These componentsinfluence the gelling, drying, and/or curing steps during the sol gelsynthesis, thus affecting the properties of the final material, such asdensity and morphology. It has been found that such gelling, drying,and/or curing control agents may help to obtain a film, rather than acolloidal structure, of the final material. Appropriate amounts of theseadditives may be determined by routine experimentation.

In an embodiment of the invention, in a method for synthesizingamorphous LLZO, quantities of a lanthanum alkoxide, a lithium alkoxide,and a zirconium alkoxide are dissolved in a quantity of an alcohol-basedsolvent to produce a mixture. A suitable lanthanum alkoxide is lanthanummethoxyethoxide, a suitable lithium alkoxide is lithium butoxide, asuitable zirconium alkoxide is zirconium butoxide, and a suitablealcohol-based solvent is methoxyethanol. The solutes and solvent aremixed in quantities and percentages to bring about substantiallycomplete dissolution. The mixture (the precursor solution formed bymixing) is dispensed into a substantially planar configuration,processed through a “gel” phase, dried and cured to a substantially dryphase.

SYNTHESIS EXAMPLES

The ingredients in the examples described below are readily-obtainablechemical compositions that may be purchased from many different chemicalsuppliers in the United States such as Gelest, Inc. (Morrisville, Pa.)and Alfa Aesar (Ward Hill, Mass.).

Lithium butoxide is also know as lithium tert-butoxide (LTB); lithiumt-butoxide; lithium tert-butoxide; lithium tert-butylate;2-methyl-2-propanolithium salt; 2-methyl-2-propanol lithium salt;lithium tert-butanolate; tert-butoxylithium; tert-butylalcohol, lithiumsalt; lithium tert-butoxide solution; lithium butoxide min off whitepowder; and lithium 2-methylpropan-2-olate. It has the molecular formulaC₄H₉LiO. It in particular may be purchased from Gelest, Inc.

Lanthanum methoxyethoxide is also known as lanthanum (III)2-methoxyethoxide, lanthanum 2-methoxyethoxide; lanthanummethoxyethoxide; lanthanum methoxyethylate; and lanthanumtri(methoxyethoxide). It has the molecular formula C₉H₂₁LaO₆. It inparticular may be purchased from Gelest, Inc.

Zirconium butoxide is also known as 1-butanol, zirconium(4+) salt;butan-1-olate, zirconium(4+); butyl alcohol, zirconium(4+) salt; butylzirconate; butyl zirconate(IV); tetrabutoxyzirconium; tetrabutylzirconate; zirconic acid butyl ester; zirconium tetrabutanolate; andzirconium tetrabutoxide. It has the molecular formula C₁₆H₃₆O₄Zr. It inparticular may be purchased from Gelest, Inc.

Methoxyethanol is also known as 2-methoxyethanol (2ME); ethylene glycolmonomethyl ether (EGME) and methyl cellosolve. It has the molecularformula C₃H₈O₂. It in particular may be purchased from Alfa Aesar.

After thorough mixing of the ingredients and substantially completedissolution of the solutes, the resulting mixture is processed through afluidized stage that includes, at least briefly, aspects of a gel state.The fully-mixed, applied and processed components produce an amorphoussubstrate of LLZO.

In the amorphous LLZO compound of the invention, the number of atoms oflithium, lanthanum, zirconium, and oxygen are proportional to oneanother within ranges as set forth in the table of Atomic Percentage(s)below. For convenience, the amorphous compound is referred to hereinsimply as LLZO although the compound may also contain carbon as a resultof the synthesis process. Further, for convenience, the compound may bedenoted by the general formula Li_(w)La_(x)Zr_(y)O_(z) wherein w, x, y,and z are positive numbers, including various combinations of integersand fractions or decimals representative of the proportionalrelationship of the elements to one another.

Carbon as Additional Element

The production techniques described herein for producing amorphous LLZOmay produce a product that contains some quantity of carbon. The carbonis left over as a by-product from one or more of the organiccompositions used as precursors in formulating the amorphous LLZO. Theatomic percentage of carbon in the amorphous composition is in the rangefrom 0.0% to about 25%. Thus, as previously explained, LLZO may often bemore correctly referred to as LCLZO.

The percentages of the number of atoms of each element as a proportionof the total number of atoms in the amorphous composition is as shown inthe following table:

Chemical Element in Amorphous Atomic Percentage of Each CompositionElement in the Composition Lithium from about 0.1% to about 50%Lanthanum from about 0.1% to about 25% Zirconium from about 0.1% toabout 25% Oxygen from about 30% to about 70% Carbon from 0.0% to about25%

Example 1 Production of Amorphous LLZO Electrolyte Medium

An amorphous LLZO precursor solution was prepared by dissolving about4.5 grams of a lanthanum methoxyethoxide solution, about 0.65 gram oflithium butoxide and about 0.77 gram of a zirconium butoxide solution inabout 5 grams of methoxyethanol.

Lanthanum methoxyethoxide and zirconium butoxide were used in solutionform for convenience in mixing. However, the invention encompasses theuse of these compositions without being pre-dissolved. The lanthanummethoxyethoxide solution comprised lanthanum methoxyethoxidepre-dissolved in methoxyethanol whereby lanthanum methoxyethoxidecomprised approximately 12% by weight of the total weight of thelanthanum methoxyethoxide solution. Similarly, the zirconium butoxidesolution comprised zirconium butoxide pre-dissolved in butanol wherebyzirconium butoxide comprised approximately 80% by weight of thezirconium butoxide solution.

The components may be mixed in any sequence, as the sequence of mixingis not significant. The thoroughly-mixed precursor solution was left ina bottle in a dry environment for about 1 to 1.5 hours to helpfacilitate substantially complete dissolution of the lithium butoxide,the component that was not pre-dissolved. What is meant by “dryenvironment” is that moisture in the ambient air is low enough thatlithium components are not degraded due to moisture.

Example 1(A) Formation of Film by Spin Coating

The precursor solution prepared in Example 1 was deposited by knownspin-coating processes at approximately 1200 rpm for about 15 seconds ina dry environment. The resulting layer of composition was placed in aclosed container and exposed to an ozone-rich air environment (ozoneconcentration larger than 0.05 part per million (ppm)) for approximately1 hour.

The term “environment” refers to the enclosed space in which a process(or sub-process) is carried out in the methodology taught by theinvention. A vaporous or gaseous element or composition in the enclosurefacilitates the drying, curing or other desired chemical processing. Agas or vapor may be placed in a suitable enclosure by known chemicalprocessing means. For example, a vapor or gas may be injected through aport. As a further example, a liquid may be placed in the enclosure andpermitted (or caused) to vaporize, thereby creating the desired vaporousor gaseous environment. In this step, as an alternative, the closedenvironment may be solvent-vapor-rich (for example wherein a quantity ofa solvent such as methoxyethanol is disposed in the closed container ina liquid phase and permitted or caused to vaporize). As anotheralternative, the closed environment may contain a gaseous mixture ofozone-rich air and solvent-vapor-rich air.

This was followed by heating at approximately 80° C. for about 30minutes, also in an ozone-rich air environment. The LLZO coating andsubstrate were then heated at approximately 300° C. for 30 minutes inair. It is to be understood that the heating times and environmentalfactors such as humidity, temperature, and gaseous content of ambientair may be varied.

The described spin-coating process resulted in an amorphous LLZO layerwhose thickness was approximately 250 nm. Thicker films or layers ofamorphous LLZO may be formed by repeating the basic spin-coatingprocessing steps multiple times until the desired thickness is achieved.

Example 1(B) Formation of Film by Casting

A LLZO precursor solution described in Example 1 was optionally heatedat approximately 100° C. under an inert gas to increase the density andviscosity of the solution. This optional step was utilized in somesamples that were produced.

The amorphous LLZO precursor solution was cast on a suitable substratethat facilitated support and then selective release of the formed layer.The layer that was formed was initially a solution. After furtherprocessing the layer may transition into a film, or a powder, or acombination of two or more of solution, film and powder. Thefreshly-cast LLZO was placed in a closed container and exposed toozone-rich air environment (ozone concentration larger than 0.05 ppm)for approximately 1 hour, although longer exposure times may be used aswell. In this step, as an alternative, the closed environment may besolvent-vapor-rich (for example wherein a quantity of a solvent such asmethoxyethanol is disposed in the closed container in a liquid phase andallowed to and/or caused to vaporize). As another alternative, theclosed environment may contain a mixture of ozone-rich air andsolvent-vapor-rich air. This was followed by heating at approximately80° C. for 30 minutes or longer, also in an ozone-rich air environment.The LLZO material was then heated at approximately 300° C. for 30minutes in air. It should be understood that the heating times andenvironmental factors such as humidity, temperature, and gaseous contentof ambient air may be varied. The immediately-above described processingstep for the layer of cast material may result in a thick layer ofamorphous LLZO or amorphous LLZO powder, or, to some degree, a thinfilm.

Example 2 of Production of Amorphous LLZO ElectrolyteMedium—Incorporation of PVP into Precursor

The LLZO precursor solution was prepared in the following fashion.First, a quantity of a polymer, polyvinyl pyrrolidone (PVP), generallynot exceeding 2 grams, was added to about 5 grams of methoxyethanol(2ME) and the mixture was allowed to sit for approximately 1 hour sothat the PVP could be fully dissolved and form a substantiallyhomogeneous PVP/2ME solution. Then about 4.5 grams of lanthanummethoxyethoxide solution, about 0.65 gram of lithium butoxide and about0.77gram of zirconium butoxide solution were dissolved in about 5 gramsof methoxyethanol and approximately 1 gram of the PVP/2ME solution.

Predissolution of PVP in 2ME is not required but may be carried out inthis manner for convenience in mixing. For example, a suitable amount ofPVP may be added to 2ME at the same time that the other solutioncomponents such as lanthanum methoxyethoxide and zirconium butoxide aremixed together in the solvent. The order of mixing has no bearing on thefinal composition and function of the solution.

As in Example 1, lanthanum methoxyethoxide and zirconium butoxide wereprovided in solution form for convenience in mixing. The invention alsoencompasses use of these compositions without being pre-dissolved. Thelanthanum methoxyethoxide solution comprised lanthanum methoxyethoxidepre-dissolved in methoxyethanol whereby lanthanum methoxyethoxidecomprised approximately 12% by weight of the total weight of thelanthanum methoxyethoxide solution. Similarly, the zirconium butoxidesolution comprised zirconium butoxide pre-dissolved in butanol wherebyzirconium butoxide comprised approximately 80% by weight of thezirconium butoxide solution.

The components may be mixed in any sequence as the sequence of mixing isnot significant. The thoroughly-mixed precursor solution was left in abottle in a dry environment for about 1 to 1.5 hours to help facilitatesubstantially complete dissolution of the lithium butoxide, thecomponent that was not pre-dissolved.

The LLZO precursor solution containing some PVP may be dispensed into asubstrate configuration by either spin coating or casting as describedin Example 1 above. Spin coating was done at approximately 1200 rpm forabout 15 seconds. Both spin coating and casting are done in a dryenvironment. The freshly-coated LLZO was placed in a closed containerand exposed to ozone-rich air environment (ozone concentration largerthan 0.05 ppm) for approximately 1 hour. In this step, as analternative, the closed environment may be solvent-vapor-rich (forexample wherein a quantity of a solvent such as methoxyethanol, inliquid phase, is disposed in the closed container and permitted orcaused to vaporize). As another alternative, the closed environment maycontain a mixture of ozone-rich air and a solvent-vapor-rich air. Thiswas followed by heating at approximately 80° C. for 30 minutes, also inan ozone-rich air environment. The LLZO coating and substrate were thenheated at approximately 300° C. for 30 minutes in air. It should beunderstood that the heating times and environmental factors such ashumidity, temperature, and gaseous content of ambient air may be varied.The immediately preceding processing step results in a layer or powderof amorphous LLZO that also contains a small PVP component.

Alternative Embodiments

The invention may be practiced by synthesizing an amorphous compound inwhich a different element is substituted for one or more of theconstituent elements of the amorphous LLZO compound. Thus, the inventionmay also be practiced by fully or partially substituting for lithium,one or more chemical elements from the alkali metal family (or group) ofthe Periodic Table such as, but not limited to, potassium and sodium.The invention also may be practiced by fully or partially substitutingfor lanthanum one or more chemical elements from the group consisting ofbarium, strontium, calcium, indium, magnesium, yttrium, scandium,chromium, aluminum, elements in the alkali metal family (or group) ofthe Periodic Table such as, but not limited to potassium, and otherelements in the lanthanoid (also know as lanthanide) series of thePeriodic Table, such as but not limited to, for example, cerium andneodymium. The invention also may be practiced by fully or partiallysubstituting for zirconium one or more chemical elements from the groupconsisting of tantalum, niobium, antimony, tin, hafnium, bismuth,tungsten, silicon, selenium, gallium and germanium. And, lastly, theinvention further may be practiced by fully or partially substitutingfor oxygen, one or more elements from the group consisting of sulfur,selenium, and the halogen family (or group) of the Periodic Table.

Alternative Processing

All or some of the processing steps during spin coating and insubsequent processing may be carried out in either pure ozone (O₃) or anozone-enriched air environment that is provided. Or, as a furtheralternative the environment may be solvent-vapor-rich (for examplewherein a quantity of a solvent such as methoxyethanol is disposed inthe closed container). As another alternative, the environment maycontain a mixture of ozone-rich air and solvent-vapor-rich air.

Two sol-gel-type related preparation processes have been describedabove, namely, one directed to spin-coating for making thin films, andthe other directed to casting for making thick layers or powder. Theinvention also may be practiced by employing other sol-gel andnon-sol-gel related processes for depositing at least one layer ofcomposition that ultimately results in the production of at least onelayer of amorphous lithium lanthanum zirconium oxide. Such additionaldepositing processes include but are not limited to dip coating, spraycoating, screen printing or ink-jet printing as well as various forms ofsputtering, chemical vapor deposition (CVD) and other fabrication anddeposition techniques.

Representative Test Results and Analytical Data for Amorphous LLZOProduced

The table below shows depth profile of composition for a typicalamorphous LLZO thin film produced under the invention. The datapresented are in the form of atomic percentages of the constituentatoms. The depth profile was achieved by sputtering away the exposedLLZO film surface at an approximate rate of 0.3 nm/s. The table wasconstructed from the X-ray photoemission spectroscopy (XPS) results thatare presented in FIG. 2. In the table, “3d” and “1s” are energy levelsubshell designations.

Depth Profile of Composition of an Amorphous LLZO Film

Sputter Atomic Concentration % time (s) La 3d O 1s C 1s Zr 3d Li 1s 02.5 37.2 32.0 3.7 24.6 200 10.3 49.6 8.3 10.0 21.8 400 10.6 53.3 10.010.0 16.1 600 8.9 50.5 8.9 8.5 23.2 800 9.2 51.9 9.4 8.9 20.6 1000 8.145.8 7.8 7.5 30.8 1200 8.1 47.4 8.3 7.8 28.4 1400 8.8 46.7 7.1 7.8 29.61600 8.6 47.0 8.5 8.0 27.9 1800 9.7 49.2 8.0 8.8 24.5 2000 9.8 48.7 8.28.9 24.3

Referring now to FIG. 2, therein are shown XPS spectra graphs for atomicspecies constituting an amorphous LLZO film. The set of spectra for eachatom corresponds to the set of depth profiling produced by sputteringtimes discussed and shown in the table above. In the graphs of FIG. 2,each horizontal axis (x-axis) displays “Binding Energy” measured inelectron volts (eV) and each vertical axis (y-axis) displays “intensity”measured in “counts per second” (cps).

Referring now to FIG. 3, the ionic conductivity of amorphous LLZOproduct as taught by the invention was observed. Ionic conductivity ofan amorphous LLZO thin film was measured by electrochemical impedancespectroscopy (EIS) taking high frequency real-axis intercept as thelithium ionic resistance of the sample from which the ionic conductivitywas estimated taking the sample geometry into account. FIG. 3 showsmeasured EIS spectra of an amorphous LLZO thin film, full spectra on theleft and the real axis intercept in detail on the right. The spectra arepresented in the form of Nyquist plots. Each horizontal axis (x-axis)displays impedance (Z′) in ohms and each vertical axis (y-axis) displaysimpedance (Z″) in ohms. The impedance that is measured by the EIS methodis a complex number having both a real and an imaginary component. Thereal portion is displayed as impedance Z′ on the horizontal axis and theimaginary portion is displayed as impedance Z″ on the vertical axis.

The EIS results indicate pure ionic conductivity of the sample, i.e., noevidence of electronic conductivity is observed. The ionic conductivity,estimated from the sample's film thickness of approximately 1.25 μm andarea of 1 mm², is in the range 1 to 2 E−3 S/cm. This conductivity isvery high for room-temperature ionic conductivity of an inorganicelectrolyte.

Example 3 Preparation and Analysis of Amorphous LLZO by Sol Gel withPartial Substitution by Aluminum

An amorphous LLZO film with partial substitution by aluminum wasprepared by mixing a sol gel precursor solution, depositing the solutionby spin coating, gelling, drying and curing of the spin coated film. Theionic conductivity of the film was then measured.

The sol gel precursor solution was prepared by mixing in an inertenvironment 10 grams of methoxyethanol (2ME) with 9 grams of lanthanummethoxyethoxide solution (about 12% by weight in methoxyethanol(LaMOE-2ME), 1.32 grams of lithium butoxide (LiOBu), 1.53 gramszirconium butoxide solution (ZrOBu, about 80% by weight in butanol) and1 gram of aluminum t-butoxide. The sol gel precursor solution wasdeposited as a film on a glass substrate with sputtered aluminum bars byspin coating in a low humidity, ozone rich air environment. The justdeposited sol gel film was exposed to the low humidity, ozone rich airenvironment for about 1 hour, followed by heating the substrate and filmat 80° C. in the low humidity, ozone rich air environment for about 45minutes and then heating the substrate and film at 135° C. in the lowhumidity, ozone rich air environment for about 45 minutes. The curing ofthe sol gel film was completed by heating the substrate and film atabout 300° C. in air for about 1 hour.

Gold bars were sputtered on top of the sol gel deposited film in anorientation perpendicular to the Al bars to form the second electrodefor conductivity measurements. The ionic conductivity was measured byelectrochemical impedance spectroscopy (EIS) using a Solartron SI 1260Impedance Analyzer instrument in the frequency range from 32 MHz to 1Hz.The ionic conductivity was estimated from the value of the highfrequency intercept of the Nyquist plot of the EIS spectra. FIGS. 3 and4 show the Nyquist plot of the measured EIS spectra; FIG. 3 showing thewhole spectrum, indicating pure ionic conduction of the film, and FIG.4, focusing on the high frequency real axis intercept. The ionicconductivity of the amorphous LLZO film with partial substitution byaluminum and prepared by sol gel was estimated to be 1.4E−4 S/cm.

Example 4 Preparation and Analysis of Amorphous LLZO by Sol Gel withPartial Substitution by Barium

An amorphous LLZO film with partial substitution by barium was preparedas described in Example 3 with the exception of the amount and type ofthe metal precursors in the sol gel precursor solution. A solution wasprepared with 6 grams of LaMOE-2ME, 1.32 grams of LiOBu, 1.53 grams ofZrOBu and 1 gram of barium methoxypropoxide solution (about 25% byweight in methoxypropanol). The Nyquist plot was similar to the Nyquistplot for Example 4, indicating pure ionic conduction. The ionicconductivity of the amorphous LLZO film with partial substitution bybarium and prepared by sol gel was estimated to be 1.8E−4 S/cm.

Example 5 Amorphous LLZO by Sol Gel with Partial Substitution byTantalum (a)

An amorphous LLZO film with partial substitution by tantalum wasprepared as described in Example 3 with the exception of the amount andtype of the metal precursors in the sol gel precursor solution. Asolution was prepared with 9 grams of LaMOE-2ME, 1.32 grams of LiOBu,1.13 grams of ZrOBu and 0.47 grams of tantalum ethoxide. The Nyquistplot was similar to the Nyquist plot for Example 3, indicating pureionic conduction. The ionic conductivity of the amorphous LLZO film withpartial substitution by tantalum and prepared by sol gel was estimatedto be 3.9E−4 S/cm.

Example 6 Amorphous LLZO by Sol Gel with Partial Substitution byTantalum (b)

An amorphous LLZO film with partial substitution by tantalum wasprepared as described in Example 3 with the exception of the amount andtype of the metal precursors in the sol gel precursor solution. Asolution was prepared with 9 grams of LaMOE-2ME, 1.32 grams of LiOBu,1.25 grams of ZrOBu and 0.35 grams of tantalum butoxide. The Nyquistplot was similar to the Nyquist plot for Example3, indicating pure ionicconduction. The ionic conductivity of the amorphous LLZO film withpartial substitution by tantalum and prepared by sol gel was estimatedto be 4.1E−4 S/cm.

Example 7 Amorphous LLZO by Sol Gel with Partial Substitution by Niobium

An amorphous LLZO film with partial substitution by niobium was preparedas described in Example 3 with the exception of the amount and type ofthe metal precursors in the sol gel precursor solution. A solution wasprepared with 9 grams of LaMOE-2ME, 1.32 grams of LiOBu, 1.20 grams ofZrOBu and 0.40 grams of niobium butoxide. The Nyquist plot was similarto the Nyquist plot for Example 3, indicating pure ionic conduction. Theionic conductivity of the amorphous LLZO film with partial substitutionby niobium and prepared by sol gel was estimated to be 6.8E−4 S/cm.

Example 8 Amorphous LLZO by Sol Gel with Addition of Acetylacetone

An amorphous LLZO film with added acetylacetone as a gelling and curingcontrol agent was prepared by mixing of a sol gel precursor solution,deposition of the solution by spin coating, gelling, drying, and curingof the spin coated film. The ionic conductivity of the film was thenmeasured.

The sol gel precursor solution was prepared by mixing in an inertenvironment 10 grams of methoxyethanol (2ME) with 9 grams of lanthanummethoxyethoxide solution (about 12% by weight in methoxyethanol(LaMOE-2ME), 1.32 grams of lithium butoxide (LiOBu), 1.53 gramszirconium butoxide solution (ZrOBu, about 80% by weight in butanol) and0.55 grams of acetylacetone. The sol gel precursor solution wasdeposited as a film on a glass substrate with sputtered aluminum bars byspin coating in a low humidity, ozone rich air environment. The justdeposited sol gel film was exposed to the low humidity, ozone rich airenvironment for about 1 hour, followed by heating the substrate and filmat 80° C. in the low humidity, ozone rich air environment for about 45minutes and then heating the substrate and film at 135° C. in the lowhumidity, ozone rich air environment for about 45 minutes. The curing ofthe sol gel film was completed by heating the substrate and film atabout 300° C. in air for about 1 hour.

Gold bars were sputtered on top of the sol gel deposited film in anorientation perpendicular to the Al bars to form the second electrodefor the conductivity measurements. The ionic conductivity was measuredby electrochemical impedance spectroscopy (EIS) using Solartron SI 1260Impedance Analyzer instrument in the frequency range from 32 MHz to 1Hz.The ionic conductivity was estimated from the value of the highfrequency intercept of the Nyquist plot of the EIS spectra. FIGS. 6 and7 show the Nyquist plot of the measured EIS spectra; FIG. 6 showing thewhole spectrum indicating pure ionic conduction of the film and FIG. 7focusing on the high frequency real axis intercept. The ionicconductivity of the amorphous LLZO film with addition of acetone andprepared by sol gel was estimated to be 5.2E−5 S/cm.

Example 9 Amorphous LLZO by Sol Gel with Lithium Acetylacetonate

An amorphous LLZO film using lithium acetylacetonate as lithiumprecursor was prepared as described in Example 8 with the exception ofthe amount and type of the metal precursors in the sol gel precursorsolution. A solution was prepared with 9 grams of LaMOE-2ME, 1.75 gramsof lithium acetylacetonate and 1.53 grams of ZrOBu. The Nyquist plot wassimilar to the Nyquist plot for Example 8, indicating pure ionicconduction. The ionic conductivity of the amorphous LLZO film usinglithium acetylacetonate as lithium precursor and prepared by sol gel wasestimated to be 1.4E−4 S/cm. Thus, lithium acetylacetonate (acac) is asuitable lithium precursor. It is expected that other metal acaccompounds and other metal β-diketonates may also be used as metalprecursors for the sol gel precursor solutions utilized in the method ofthe invention.

Example 10 Amorphous LLZO by Sol Gel with Addition of Ethanol

An amorphous LLZO film prepared using a different solvent mixture wasprepared as described in Example 8 with the exception of the amount andtype of the metal precursors in the sol gel precursor solution. Asolution was prepared with 2 grams of 2ME, 1.8 grams of LaMOE-2ME, 0.26grams of LiOBu, 0.31 grams of ZrOBu and 0.37 grams of ethanol. Theethanol was included in the solution in order to help control the solgel gellation and curing processes. The Nyquist plot was similar to theNyquist plot for Example 8, indicating pure ionic conduction. The ionicconductivity of the amorphous LLZO film with added ethanol and preparedby sol gel was estimated to be 1.6E−4 S/cm.

Example 11 Amorphous LLZO by Sol Gel with Addition of Ethanol and Water

An amorphous LLZO film prepared using a different solvent mixture wasprepared as described in Example 8 with the exception of the amount andtype of the metal precursors in the sol gel precursor solution. Asolution was prepared with 2 grams of 2ME, 1.8 grams of LaMOE-2ME, 0.26grams of LiOBu, 0.31 grams of ZrOBu and a water/ethanol solutioncontaining 6.6 milligrams of water and 0.31 grams of ethanol that hadbeen mixed prior to the preparation of the sol gel precursor solution.The ethanol/water solution was included in order to help control the solgel gellation and curing processes. The Nyquist plot was similar to theNyquist plot for Example 8, indicating pure ionic conduction. The ionicconductivity of the amorphous LLZO film with water in ethanol added andprepared by sol gel was estimated to be 3.6E−4 S/cm.

Many variations and modifications may be made to the above-describedembodiments without departing from the scope of the claims. All suchmodifications, combinations, and variations are included herein by thescope of this disclosure and the following claims.

The composition described herein is amorphous lithium lanthanumzirconium oxide (LLZO). It is ionically conductive and, ifelectronically conductive at all, only negligibly so. When formed as athin layer, the amorphous LLZO is an effective electrolyte medium thatis useful in an electrochemical cell in which lithium is employed aselectrode material. The amorphous LLZO electrolyte medium isnon-aqueous, non-liquid, inorganic, and non-reactive with lithium; willnot leak or leach with respect to adjacent components of a battery cell;and can be manufactured in flexible, thin, useful layers.

It will be appreciated by those skilled in the art that changes could bemade to the embodiments described above without departing from the broadinventive concept thereof It is understood, therefore, that thisinvention is not limited to the particular embodiments disclosed, but itis intended to cover modifications within the spirit and scope of thepresent invention as defined by the appended claims.

1. An amorphous oxide-based compound having a general formulaMwM′xM″yM′″z, wherein M comprises at least one alkali metal, M′comprises at least one element selected from the group consisting ofbarium, strontium, calcium, indium, magnesium, yttrium, scandium,chromium, aluminum, alkali metals, and lanthanides, M″ comprises atleast one element selected from the group consisting of zirconium,tantalum, niobium, antimony, tin, hafnium, bismuth, tungsten, silicon,selenium, gallium and germanium, and M′″ comprises oxygen and optionallyat least one element selected from the group consisting of sulfur,selenium, and halogens, wherein w, x, y, and z are positive numbers,including various combinations of integers and fractions or decimals. 2.The amorphous oxide-based compound of claim 1, wherein M compriseslithium, M′ comprises lanthanum, M″ comprises zirconium, and M′″comprises oxygen.
 3. The amorphous oxide-based compound of claim 1,wherein by percentage of total number of atoms M comprises from about0.1% to about 50%, M′ comprises from about 0.1% to about 25%, M″comprises from about 0.1% to about 25%, and M′″ comprises from about 30%to about 70%.
 4. The amorphous oxide-based compound of claim 1, having asubstantially planar configuration for an electrolyte medium.
 5. Anelectrolyte medium comprising at least one layer of amorphous lithiumlanthanum zirconium oxide.
 6. The electrolyte medium of claim 5, whereinsaid amorphous lithium lanthanum zirconium oxide comprises by percentageof total number of atoms from about 0.1% to about 50% lithium, fromabout 0.1% to about 25% lanthanum, from about 0.1% to about 25%zirconium, from about 30% to about 70% oxygen and from 0.0% to about 25%carbon.
 7. A sol gel method for synthesizing an amorphous oxide-basedcompound comprising: producing a mixture by substantially dissolving ina solvent, a first precursor solute comprising an alkali-metal compound,a second precursor solute comprising a compound of at least one ofbarium, strontium, calcium, indium, magnesium, yttrium, scandium,chromium, aluminum, an alkali-metal and a lanthanide, a third precursorsolute comprising a compound of at least one of zirconium, tantalum,niobium, antimony, tin, hafnium, bismuth, tungsten, silicon, selenium,gallium and germanium, and optionally a fourth precursor solutecomprising a compound of at least one of oxygen, sulfur, selenium, and ahalogen; and dispensing said mixture in a substantially planarconfiguration, transitioning through a gel phase, and drying and curingto a substantially dry phase.
 8. A method of synthesizing amorphouslithium lanthanum zirconium oxide comprising: producing a mixture bysubstantially dissolving in a solvent a first precursor solutecomprising a compound of lithium, a second precursor solute comprising acompound of lanthanum, and a third precursor solute comprising acompound of zirconium; and dispensing said mixture in a substantiallyplanar configuration and drying and curing to a substantially dry phase.9. The method of claim 8, wherein said solvent comprises analcohol-based solvent, said first precursor solute comprises lithiumalkoxide, said second precursor solute comprises lanthanum alkoxide, andsaid third precursor solute comprises zirconium alkoxide.
 10. The methodof claim 9, wherein said alcohol-based solvent comprises methoxyethanol.11. The method of claim 9, wherein said lithium alkoxide compriseslithium butoxide, said lanthanum alkoxide comprises lanthanummethoxyethoxide, and said zirconium alkoxide comprises zirconiumbutoxide.
 12. The method of claim 11, wherein said lanthanummethoxyethoxide comprises an amount of said lanthanum methoxyethoxidepre-dissolved in an amount of said alcohol-based solvent to produce alanthanum methoxyethoxide solution comprising about 12% by weight ofsaid lanthanum methoxyethoxide.
 13. The method of claim 11, wherein saidzirconium butoxide comprises an amount of said zirconium butoxidepre-dissolved in an amount of butanol to produce a zirconium butoxidesolution comprising about 80% by weight of said zirconium butoxide. 14.The method of claim 8, wherein said mixture is dispensed into asubstantially planar configuration by one of spin coating, casting, dipcoating, spray coating, screen printing and ink-jet printing.
 15. Themethod of claim 11, wherein said lanthanum methoxyethoxide comprises anamount of said lanthanum methoxyethoxide pre-dissolved in an amount ofsaid alcohol-based solvent to produce a lanthanum methoxyethoxidesolution comprising about 12% by weight of said lanthanummethoxyethoxide; and wherein said zirconium butoxide comprises an amountof said zirconium butoxide pre-dissolved in an amount of butanol toproduce a zirconium butoxide solution comprising about 80% by weight ofsaid zirconium butoxide.
 16. The method of claim 8, wherein the mixturefurther comprises a polymer.
 17. The method of claim 16, wherein saidsolvent comprises an alcohol-based solvent, said first precursor solutecomprises lithium alkoxide, said second precursor solute compriseslanthanum alkoxide, and said third precursor solute comprises zirconiumalkoxide.
 18. The method of claim 17, wherein said alcohol-based solventcomprises methoxyethanol and said polymer comprises polyvinylpyrrolidone.
 19. The method of claim 17, wherein said lithium alkoxidecomprises lithium butoxide, said lanthanum alkoxide comprises lanthanummethoxyethoxide, and said zirconium alkoxide comprises zirconiumbutoxide.
 20. The method of claim 19, wherein said lanthanummethoxyethoxide comprises an amount of said lanthanum methoxyethoxidepre-dissolved in an amount of said alcohol-based solvent to produce alanthanum methoxyethoxide solution comprising about 12% by weight ofsaid lanthanum methoxyethoxide.
 21. The method of claim 19, wherein saidzirconium butoxide comprises an amount of said zirconium butoxidepre-dissolved in an amount of butanol to produce a zirconium butoxidesolution comprising about 80% by weight of said zirconium butoxide. 22.The method of claim 16, wherein said polymer comprises an amount of saidpolymer pre-dissolved in an amount of said alcohol-based solvent toproduce a polymer solution.
 23. The method of claim 7, wherein saidmixture is dispensed into a substantially planar configuration by one ofspin coating, casting, dip coating, spray coating, screen printing andink-jet printing.
 24. The method of claim 19, wherein said lanthanummethoxyethoxide comprises an amount of said lanthanum methoxyethoxidepre-dissolved in an amount of said alcohol-based solvent to produce alanthanum methoxyethoxide solution comprising about 12% by weight ofsaid lanthanum methoxyethoxide; wherein said zirconium butoxidecomprises an amount of said zirconium butoxide pre-dissolved in anamount of butanol to produce a zirconium butoxide solution comprisingabout 80% by weight said zirconium butoxide; and wherein said polymercomprises an amount of said polymer pre-dissolved in an amount of saidalcohol-based solvent to produce a polymer solution.
 25. The method ofclaim 24, wherein said alcohol-based solvent comprises methoxyethanoland said polymer comprises polyvinyl pyrrolidone.
 26. The method ofclaim 7, wherein the step of drying and curing said mixture comprisesexposing and heating said mixture in an environment comprising air andozone, wherein a concentration of said ozone in said air is greater than0.05 parts per million.
 27. The method of claim 26, wherein the step ofdrying and curing said mixture further comprises: exposing said mixtureto said environment comprising air and ozone for about one hour; andthen heating said mixture in said environment comprising air and ozoneat about 80° C. for about 30 minutes.
 28. The method of claim 27,wherein the steps of exposing and heating said mixture in an environmentcomprising air and ozone are followed by the step of heating saidmixture in air.
 29. The method of claim 28, wherein the step of dryingand curing said mixture further comprises heating said mixture in air atabout 300° C. for about 30 minutes.
 30. The method of claim 7, whereinthe step of drying and curing said mixture comprises exposing andheating said mixture in an environment comprising air and ozone, whereina concentration of said ozone in said air is greater than 0.05 parts permillion.
 31. The method of claim 30, wherein the step of drying andcuring said mixture further comprises: exposing said mixture to saidenvironment comprising air and ozone for about one hour; and thenheating said mixture in said environment comprising air and ozone atabout 80° C. for about 30 minutes.
 32. The method of claim 30, whereinthe steps of exposing and heating said mixture in an environmentcomprising air and ozone are followed by the step of heating saidmixture in air.
 33. The method of claim 32, wherein the step of dryingand curing said mixture further comprises: exposing said mixture to saidenvironment comprising air and ozone for about one hour; then heatingsaid mixture in said environment comprising air and ozone at about 80°C. for about 30 minutes; and then heating said mixture in air at about300° C. for about 30 minutes.
 34. The method of claim 16, wherein thestep of drying and curing said mixture comprises exposing and heatingsaid mixture in an environment comprising air and ozone, wherein aconcentration of said ozone in said air is greater than 0.05 parts permillion.
 35. The method of claim 34, wherein the step of drying andcuring said mixture further comprises: exposing said mixture to saidenvironment comprising air and ozone for about one hour; and thenheating said mixture in said environment comprising air and ozone atabout 80° C. for about 30 minutes.
 36. The method of claim 34, whereinthe steps of exposing and heating said mixture in an environmentcomprising air and ozone are followed by the step of heating saidmixture in air.
 37. The method of claim 36, wherein the step of dryingand curing said mixture further comprises: exposing said mixture to saidenvironment comprising air and ozone for about one hour; then heatingsaid mixture in said environment comprising air and ozone at about 80°C. for about 30 minutes; and then heating said mixture in air at about300° C. for about 30 minutes.
 38. An amorphous oxide-based compoundhaving a general formula MwCM′xM″yM′″z, wherein C comprises carbon, Mcomprises at least one alkali metal, M′ comprises at least one elementselected from the group consisting of barium, strontium, calcium,indium, magnesium, yttrium, scandium, chromium, aluminum, alkali metals,and lanthanides, M″ comprises at least one element selected from thegroup consisting of zirconium, tantalum, niobium, antimony, tin,hafnium, bismuth, tungsten, silicon, selenium, gallium and germanium,and M′″ comprises oxygen and optionally at least one element selectedfrom the group consisting of sulfur, selenium, and halogens, wherein w,x, y, and z are positive numbers, including various combinations ofintegers and fractions or decimals.
 39. The amorphous oxide-basedcompound of claim 38, wherein M comprises lithium, M′ compriseslanthanum, M″ comprises zirconium and M′″ comprises oxygen.
 40. Theamorphous oxide-based compound of claim 38, wherein by percentage oftotal number of atoms M comprises from about 0.1% to about 50%, carboncomprises up to about 25%, M′ comprises from about 0.1% to about 25%, M″comprises from about 0.1% to about 25%, and M′″ comprises from about 30%to about 70%.
 41. The amorphous oxide-based compound of claim 38, havinga substantially planar configuration for an electrolyte medium.
 42. Anelectrolyte medium comprising at least one layer of amorphous lithiumcarbon lanthanum zirconium oxide.
 43. The electrolyte medium of claim42, wherein said amorphous lithium carbon lanthanum zirconium oxidecomprises by percentage of total number of atoms from about 0.1% toabout 50% lithium, up to about 25% carbon, from about 0.1% to about 25%lanthanum, from about 0.1% to about 25% zirconium, and from about 30% toabout 70% oxygen.
 44. A method of synthesizing amorphous lithium carbonlanthanum zirconium oxide comprising: producing a mixture bysubstantially dissolving in a solvent, a first precursor solutecomprising a compound of lithium, a second precursor solute comprising acompound of lanthanum, and a third precursor solute comprising acompound of zirconium; and dispensing said mixture in a substantiallyplanar configuration and drying and curing to a substantially dry phase.45. The method of claim 44, wherein the step of drying and curing saidmixture comprises exposing and heating said mixture in an environmentcomprising air and ozone, wherein a concentration of said ozone in saidair is greater than 0.05 parts per million.
 46. The method of claim 45,wherein the step of drying and curing said mixture further comprises:exposing said mixture to said environment comprising air and ozone forabout one hour; and then heating said mixture in said environmentcomprising air and ozone at about 80° C. for about 30 minutes.
 47. Themethod of claim 45, wherein the steps of exposing and heating saidmixture in an environment comprising air and ozone are followed by thestep of heating said mixture in air.
 48. The method of claim 47, whereinthe step of drying and curing said mixture further comprises: exposingsaid mixture to said environment comprising air and ozone for about onehour; then heating said mixture in said environment comprising air andozone at about 80° C. for about 30 minutes; and then heating saidmixture in air at about 300° C. for about 30 minutes.
 49. The method ofclaim 44, wherein said solvent comprises an alcohol-based solvent, saidfirst precursor solute comprises lithium alkoxide, said second precursorsolute comprises lanthanum alkoxide, and said third precursor solutecomprises zirconium alkoxide.
 50. The method of claim 49, wherein saidalcohol-based solvent comprises methoxyethanol.
 51. The method of claim49, wherein said lithium alkoxide comprises lithium butoxide, saidlanthanum alkoxide comprises lanthanum methoxyethoxide, and saidzirconium alkoxide comprises zirconium butoxide.
 52. The method of claim51, wherein said lanthanum methoxyethoxide comprises an amount of saidlanthanum methoxyethoxide pre-dissolved in an amount of saidalcohol-based solvent to produce a lanthanum methoxyethoxide solutioncomprising about 12% by weight of said lanthanum methoxyethoxide. 53.The method of claim 51, wherein said zirconium butoxide comprises anamount of said zirconium butoxide pre-dissolved in an amount of butanolto produce a zirconium butoxide solution comprising about 80% by weightof said zirconium butoxide.
 54. The method of claim 51, wherein saidlanthanum methoxyethoxide comprises an amount of said lanthanummethoxyethoxide pre-dissolved in an amount of said alcohol-based solventto produce a lanthanum methoxyethoxide solution comprising about 12% byweight of said lanthanum methoxyethoxide; and wherein said zirconiumbutoxide comprises an amount of said zirconium butoxide pre-dissolved inan amount of butanol to produce a zirconium butoxide solution comprisingabout 80% by weight of said zirconium butoxide.
 55. The method of claim44, wherein said mixture is dispensed into a substantially planarconfiguration by one of spin coating, casting, dip coating, spraycoating, screen printing and ink-jet printing.
 56. The method of claim44, wherein the mixture further comprises a polymer.
 57. The method ofclaim 56, wherein the step of drying and curing said mixture comprisesexposing and heating said mixture in an environment comprising air andozone, wherein a concentration of said ozone in said air is greater than0.05 parts per million.
 58. The method of claim 57, wherein the step ofdrying and curing said mixture further comprises: exposing said mixtureto said environment comprising air and ozone for about one hour; andthen heating said mixture in said environment comprising air and ozoneat about 80° C. for about 30 minutes.
 59. The method of claim 57,wherein the steps of exposing and heating said mixture in an environmentcomprising air and ozone are followed by the step of heating saidmixture in air.
 60. The method of claim 59, wherein the step of dryingand curing said mixture further comprises: exposing said mixture to saidenvironment comprising air and ozone for about one hour; then heatingsaid mixture in said environment comprising air and ozone at about 80°C. for about 30 minutes; and then heating said mixture in air at about300° C. for about 30 minutes.
 61. The method of claim 56, wherein saidsolvent comprises an alcohol-based solvent, said first precursor solutecomprises lithium alkoxide, said second precursor solute compriseslanthanum alkoxide, and said third precursor solute comprises zirconiumalkoxide.
 62. The method of claim 61, wherein said alcohol-based solventcomprises methoxyethanol and said polymer comprises polyvinylpyrrolidone.
 63. The method of claim 61, wherein said lithium alkoxidecomprises lithium butoxide, said lanthanum alkoxide comprises lanthanummethoxyethoxide, and said zirconium alkoxide comprises zirconiumbutoxide.
 64. The method of claim 63, wherein said lanthanummethoxyethoxide comprises an amount of said lanthanum methoxyethoxidepre-dissolved in an amount of said alcohol-based solvent to produce alanthanum methoxyethoxide solution comprising about 12% by weight ofsaid lanthanum methoxyethoxide.
 65. The method of claim 63, wherein saidzirconium butoxide comprises an amount of said zirconium butoxidepre-dissolved in an amount of butanol to produce a zirconium butoxidesolution comprising about 80% by weight of said zirconium butoxide. 66.The method of claim 56, wherein said polymer comprises an amount of saidpolymer pre-dissolved in an amount of said alcohol-based solvent toproduce a polymer solution.
 67. The method of claim 63, wherein saidlanthanum methoxyethoxide comprises an amount of said lanthanummethoxyethoxide pre-dissolved in an amount of said alcohol-based solventto produce a lanthanum methoxyethoxide solution comprising about 12% byweight of said lanthanum methoxyethoxide; wherein said zirconiumbutoxide comprises an amount of said zirconium butoxide pre-dissolved inan amount of butanol to produce a zirconium butoxide solution comprisingabout 80% by weight of said zirconium butoxide; and wherein said polymercomprises an amount of said polymer pre-dissolved in an amount of saidalcohol-based solvent to produce a polymer solution.
 68. The method ofclaim 67, wherein said alcohol-based solvent comprises methoxyethanoland said polymer comprises polyvinyl pyrrolidone.
 69. The method ofclaim 56, wherein said mixture is dispensed into a substantially planarconfiguration by one of spin coating, casting, dip coating, spraycoating, screen printing, and ink-jet printing.
 70. The method of claim8, wherein said solvent comprises an alcohol-based solvent, and whereinat least one of said first precursor solute, said second precursorsolute, and said third precursor solute comprises a metal β-diketonate.71. The method of claim 70, wherein the metal β-diketonate comprises ametal acetyl acetonate.
 72. The method of claim 16, wherein said solventcomprises an alcohol-based solvent, and wherein at least one of saidfirst precursor solute, said second precursor solute, and said thirdprecursor solute comprises a metal β-diketonate.
 73. The method of claim72, wherein the metal β-diketonate comprises a metal acetyl acetonate.74. The method of claim 44, wherein said solvent comprises analcohol-based solvent, and wherein at least one of said first precursorsolute, said second precursor solute, and said third precursor solutecomprises a metal β-diketonate.
 75. The method of claim 74, wherein themetal β-diketonate comprises a metal acetyl acetonate.
 76. The method ofclaim 56, wherein said solvent comprises an alcohol-based solvent, andwherein at least one of said first precursor solute, said secondprecursor solute, and said third precursor solute comprises a metalβ-diketonate.
 77. The method of claim 76, wherein the metal β-diketonatecomprises a metal acetyl acetonate.
 78. The method of claim 7, whereinthe mixture further comprises at least one gelling, drying, and/orcuring control agent.
 79. The method of claim 78, wherein the at leastone gelling, drying, and/or curing control agent is selected from thegroup consisting of acetylacetone, acetic acid, ethanol, and anethanol/water mixture.
 80. The method of claim 8, wherein the mixturefurther comprises at least one gelling, drying, and/or curing controlagent.
 81. The method of claim 80, wherein the at least one gelling,drying, and/or curing control agent is selected from the groupconsisting of acetylacetone, acetic acid, ethanol, and an ethanol/watermixture.
 82. The method of claim 44, wherein the mixture furthercomprises at least one gelling, drying, and/or curing control agent. 83.The method of claim 82, wherein the at least one gelling, drying, and/orcuring control agent is selected from the group consisting ofacetylacetone, acetic acid, ethanol, and an ethanol/water mixture.